CN110075900A - The mesoporous carbon-silica catalyst material and preparation method and application of supported palladium - Google Patents
The mesoporous carbon-silica catalyst material and preparation method and application of supported palladium Download PDFInfo
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- CN110075900A CN110075900A CN201910358799.4A CN201910358799A CN110075900A CN 110075900 A CN110075900 A CN 110075900A CN 201910358799 A CN201910358799 A CN 201910358799A CN 110075900 A CN110075900 A CN 110075900A
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- palladium
- catalyst material
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- mesoporous carbon
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical compound C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- OQXVXPBDSJQYRR-UHFFFAOYSA-N 8-methoxy-2-methylquinoline Chemical compound C1=C(C)N=C2C(OC)=CC=CC2=C1 OQXVXPBDSJQYRR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 4
- 229920003987 resole Polymers 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- WBZRSFDJNJXREC-UHFFFAOYSA-N Cl[Cl]Cl Chemical compound Cl[Cl]Cl WBZRSFDJNJXREC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 229920000359 diblock copolymer Polymers 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 239000013335 mesoporous material Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DORMTBIPKNPJPY-UHFFFAOYSA-N acetic acid;iodobenzene Chemical compound CC(O)=O.IC1=CC=CC=C1 DORMTBIPKNPJPY-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000009514 concussion Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HNUQMTZUNUBOLQ-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO HNUQMTZUNUBOLQ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VSTOHTVURMFCGL-UHFFFAOYSA-N [C].O=[Si]=O Chemical compound [C].O=[Si]=O VSTOHTVURMFCGL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
Abstract
The present invention relates to the mesoporous carbon-silica catalyst materials and preparation method and application of a kind of supported palladium, this method is, using soluble resin as carbon source, organic silicon source is organo-functional group source, surfactant is template, and inorganic silicon source is added, ordered mesoporous polymer-silica composite material of amino functional is prepared by the polynary method assembled altogether；Amino functional mesoporous carbon-silica composite material is obtained through calcining；Further, dip loading Pd loads to Pd on mesoporous composite material, most obtains product through reduction afterwards.Compared with prior art, preparation method is simple by the present invention, and the palladium catalyst being prepared is used to be catalyzed the reaction of 8- methylquinoline and methanol-fueled CLC 8- methoxyl methyl quinoline, and yield is high.
Description
Technical field
The invention belongs to mesoporous material preparation technical fields, and in particular to a kind of mesoporous carbon-silica of supported palladium is urged
Agent material and preparation method and application.
Background technique
Palladium catalyst is a kind of important catalysts during organic synthesis, is answered Yu YoujiC-H key living extensively
Change in reaction and fine chemicals production.Palladium carbon is widely applied industrial catalyst.But since carbon material sheet is as inertia
Binding force between carrier, with palladium is weaker, and there are Metal Palladium loss, reunion, easy poisoning and deactivations etc. to ask for catalyst in reaction process
Topic.Therefore, a kind of stable structure is invented, inexpensive palladium catalyst replaces traditional palladium-carbon catalyst significant.
Ordered mesoporous material specific surface area with higher, biggish pore volume, uniform aperture can be widely applied to
The fields such as absorption, catalysis and separation.Using ordered mesoporous material as carrier stablize palladium nano-particles, can effectively solve it is above-mentioned not
Foot, development have attracted extensive attention.Loading palladium nano-particles by back loading mode as carrier using ordered mesoporous material is
Prepare a kind of conventional method of metallic catalyst.But this method can by the requirement of catalyst physical and chemical performance, select suitable pore structure and
The carrier of surface area, enhance catalyst mechanical performance and heat-resisting, heat transfer property；For noble metal catalyst, due to by metal
It is dispersed on high surface area, catalyst noble metal dosage can be saved, to reduce the cost of catalyst；Easily use multicomponent
It loads simultaneously, or prepares multifunction catalyst using certain function of carrier.The hybridization mesoporous material for synthesizing organic functional can
With the functionalization in hole surface and duct space, stronger combination between functional group and palladium can be in catalyst pyrocarbon
Dispersion, stable palladium species, final catalyst have palladium nano-particles high degree of dispersion, size smaller and higher during changing
Stability.
Patent CN102660028A discloses a kind of organic group functionized ordered mesoporous polymer material and its synthesis side
Method, the material organic functional mass contg height (0.1wt%~15wt%), specific surface area height (200~500m2/ g), Kong Rong great
(0.1~1.0cm3/ g), aperture it is uniform (3~12nm), there is two-dimentional six sides or three-dimensional cubic mesoscopic structure.Its synthetic method
It include: in acid condition, inorganic silicon source and the organic silicon source containing organo-functional group to be subjected to prehydrolysis；Then with nonionic
Surfactant mixing；Soluble resin is added and carries out self assembly in organic solution, obtains organic group functionized-nonionic
Surfactant composite material.Surfactant is removed, organic group functionized ordered mesoporous polymer material is obtained.The patent
It is not yet used for the preparation of amino functional carbon-silicon dioxide carried palladium catalyst, and the functionalization catalyst prepared to be unused
The verifying of the catalyst performance is carried out in reaction.
Summary of the invention
The purpose of the present invention is to solve the above-mentioned problems and provides a kind of mesoporous carbon-silica catalysis of supported palladium
Agent material and preparation method and application, preparation method is simple for this, and low in cost, catalyst performance is excellent.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium, this method be,
Using soluble resin as carbon source, organic silicon source is organo-functional group source, and surfactant is template, and nothing is added
Machine silicon source prepares ordered mesoporous polymer-silica composite material of amino functional by the polynary method assembled altogether；
Amino functional mesoporous carbon-silica composite material is obtained through calcining；
Further, dip loading Pd loads to Pd on mesoporous composite material；
Most product is obtained through reduction afterwards.
Preferably, the soluble resin is resol resin of the molecular weight between 200-5000g/mol, into one
Preferably, the resol resin is resol to step.
Preferably, the organic silicon source is selected from N, N- bis- (3- trimethoxy silicon propyl) urea, 3- ureido-propyl trimethoxy
Silane, 3- ureidopropyltriethoxysilane, 3- TSL 8330, in 3-aminopropyltriethoxysilane
It is one or more.
Preferably, the inorganic silicon source is selected from one of ethyl orthosilicate, methyl orthosilicate or positive silicic acid propyl ester or more
Kind.
Preferably, the surfactant is nonionic surfactant, is selected from polyethylene oxide-polypropylene oxide three
One of block copolymer or alkane-polyethylene oxide diblock copolymer surfactant are a variety of, and general formula can be used
CaH2a+1EOb、EOcPOdEOcIt indicates, wherein a numberical range is 10-18, b 5-25, c 5-135, d 25-135；Further
Preferably, the surfactant is C16H33EO10(Brij56)、C16H33EO20、C18H37EO10(Brij76)、EO20PO70EO20
(P123)、EO106PO70EO106(F127) or EO132PO50EO132One or more of (F108).Surfactant can be from BASF
Or Sigma-Aldrich is obtained.
A kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium, specifically includes the following steps:
(1) it dissolves each other surfactant and hydrochloric acid to obtain solution A, hydrolyzes inorganic silicon source with organic solvent and organic silicon source obtains
To solution B, solution A and solution B are mixed and added into soluble resin and reacted, the organic solvent contained in reactant is gone
It removes, obtains solid；
(2) solid for obtaining step (1) carries out low temperature thermosetting, preformed material is obtained, by preformed material in inert atmosphere
The lower calcining of protection removes surfactant, obtains catalyst material predecessor；
(3) the catalyst material predecessor of step (2) is mixed with palladium ion solution, solid is obtained by filtration, by reduction
Obtain the mesoporous carbon-silica catalyst material of supported palladium.
Preferably, the organic solvent is selected from one of alcohols, benzene class, tetrahydrofuran, ether or methylene chloride or more
Kind；
The mass concentration of surfactant is 0.5%-25% in step (1), and the concentration of hydrochloric acid solution is 0.2-4mol/L,
The molar ratio of inorganic silicon source and organic silicon source is 1-20, further preferably 1-10, the dosage of organic silicon source and surfactant
Molar ratio is 10-60, and the molar ratio of soluble resin and total silicon source is 0.01-0.6；
Hydrolysis temperature is 20-45 DEG C, hydrolysis time 0.5-4h in step (1), and reaction temperature is 20~45 DEG C, when reaction
Between be 10min-4h.
Preferably, step (2) low temperature thermoset temperature is 40-120 DEG C, and the low temperature thermosetting time is 12-48h, and calcination temperature is
200-500 DEG C, calcination temperature 1-12h；
Step (3) is using hydrogen reducing or using formalin, sodium borohydride solution or solution of potassium borohydride low-temperature reduction；
Palladium ion solution in step (3) is selected from palladium acetate, palladium nitrate, two ammino palladium of dichloro, four ammino palladium of dichloro, chlorine palladium
One of sour sodium or chlorination palladium reagent are a variety of.
The catalyst material that above-mentioned preparation method is prepared, the catalyst material have six Fang Jie of two dimension of high-sequential
Structure is seen, specific surface area is 300~900m20.30~2.0cm of/g, Kong Rongwei3/ g, aperture are 5.0~15.0nm, and metal Pd contains
Amount is 1~10wt%, and Pd nanoparticle size is 1~5.0nm.
The catalyst material generates the application of 8- methoxyl methyl quinoline in 8- methylquinoline and methanol reaction.
The present invention utilizes solvent evaporation induced self-assembly technology, using phenolic resin as carbon source, 3- aminopropyl trimethoxy
Silane is organo-functional group source, and ethyl orthosilicate is inorganic silicon source, and triblock copolymer is template, is assembled altogether by polynary
Method prepares ordered mesoporous polymer-silica composite material of amino functional.Further utilize Pd-N coordination by Pd
It loads on mesoporous polymer, obtains amino functional through low temperature sodium borohydride solution or high-temperature hydrogen reduction Pd nano particle
Mesoporous carbon-silica composite material loaded palladium catalyst.This catalyst is used to be catalyzed 8- methylquinoline and methanol occurs
Sp3C-H functionalization constructs C-O key and generates the reaction of 8- methoxyl methyl quinoline, can get 87% yield, has been higher than homogeneous catalyst
The result (yield 77%) for having document report optimal.
Compared with prior art, the invention has the following advantages:
(1) preparation method of the invention includes the routine operations such as mixing, reaction, calcining and filtering, simple and easy, and is used
Raw material be common drug, it is at low cost；
(2) palladium catalyst being prepared has two-dimentional six side's mesoscopic structures, and specific surface area is larger, and pore volume is big, aperture
Uniform, the palladium content of load is high, and palladium nano-particles partial size is small, has excellent structure；
(3) this palladium catalyst is used for the reaction on 8- methylquinoline and methanol GCMS computer 8- methoxyl methyl quinoline, yield
It is high.
Detailed description of the invention
Fig. 1 is six side of two dimension (p6mm) carbon-earth silicon material distinctive X-ray diffraction (XRD) prepared by embodiment 2
Spectrogram；
Fig. 2 is the feature nitrogen adsorption-desorption of six side of two dimension (p6mm) carbon-earth silicon material prepared by embodiment 2
Isollaothermic chart；
Fig. 3 is distinctive X-ray diffraction (XRD) spectrogram of mesoporous carbon-silica palladium catalyst prepared by embodiment 3；
Fig. 4 is transmission electron microscope (TEM) figure of mesoporous carbon-silica palladium catalyst prepared by embodiment 3；
Fig. 5 is distinctive X-ray diffraction (XRD) spectrogram of mesoporous carbon-silica palladium catalyst prepared by embodiment 4；
Fig. 6 is distinctive X-ray diffraction (XRD) spectrogram of mesoporous carbon-silica palladium catalyst prepared by embodiment 5.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
6.0g phenol is put in three-neck flask, 50 DEG C of heating water baths make its transparent liquid；Preparing mass percent is
20% sodium hydroxide solution 3.70g, slowly instills in the liquid.After ten minutes, the first that mass percentage is 37% is added
Aldehyde solution 15.0g, 90 DEG C are flowed back 1 hour, are cooled to room temperature, and adjust pH to neutrality.It is evaporated under reduced pressure, obtains under the conditions of 45-50 DEG C
Obtaining residue is target product phenolic resin.After being cooled to room temperature, it is made into the phenolic aldehyde that mass percentage concentration is 20-45wt% respectively
The ethyl alcohol or diethyl ether solution of resin prepolymer are spare.
Embodiment 2
At 40-60 DEG C, the F127 (EO of 2.0g106PO70EO106) surfactant is dissolved in 10.0g dichloromethane solution,
1g 0.4mol/L hydrochloric acid solution is then added, stirs prehydrolysis 1 hour, obtains solution A.At identical temperature, in 10.0g dichloromethane
3.0g ethyl orthosilicate is sequentially added in alkane solution, 1.2g N, N- bis- (3- trimethoxy silicon propyl) urea is stirred 1 hour, obtained molten
Liquid B.After solution A and B solution mixing, the phenolic resin synthesized in addition 20wt% step 1, magnetic agitation 4 hours.It obtains pale yellow
The transparent clear solution of color.Above-mentioned solution is uniformly layered on glass culture dish surface, is placed 2 hours at room temperature, later, by temperature
It rises to 100 DEG C of hot polymerizations 24 hours, flaxen transparent membrane is scraped, i.e. preformed material.
Obtained preformed material is calcined into 6 hours removing surfactants with inertia protection gas under the conditions of 400 DEG C of temperature.
Obtained material is amino functional mesoporous carbon-silica material.This material has the structure (space group of two-dimentional six sides
P6mm), aperture 10nm, Kong Rongwei 1.93cm3/ g, specific surface area 874m2/g.Its distinctive X-ray diffraction (XRD) map such as Fig. 1
It is shown.Its nitrogen adsorption-desorption isotherm figure is as shown in Figure 2.
Embodiment 3
At 40-60 DEG C, the P123 (EO of 2.0g20PO70EO20) surfactant is dissolved in 10.0g tetrahydrofuran solution,
1g 1mol/L hydrochloric acid solution is then added, stirs prehydrolysis 1 hour, obtains solution A.At identical temperature, in 10.0g tetrahydrofuran
3.6g positive silicic acid propyl ester is sequentially added in solution, 1.0g 3- ureidopropyltriethoxysilane stirs 1 hour, obtains solution B.A
After solution and B solution mixing, the phenolic resin synthesized in addition 20wt% embodiment 1, magnetic agitation 4 hours.It obtains light yellow
Transparent clear solution.Above-mentioned solution is uniformly layered on glass culture dish surface, is placed 2 hours at room temperature, later, by temperature liter
To 100 DEG C hot polymerization 24 hours, flaxen transparent membrane is scraped, i.e. preformed material.Preformed material inertia is protected gas by 400 DEG C
Calcine 6 hours removing surfactants.
It weighs the above-mentioned solid sample of 0.5g to be placed in moderate beaker, the palladium chloride solution (1g/ of 2.2mL is added
100mL).Sealing places it in constant temperature oscillator, and concussion is uniform at room temperature.Sodium borohydride solution is proportionally added into after taking-up,
It continuously adds and shakes up half an hour in constant temperature oscillator.It then takes out and is placed on indoor solvent flashing, after solvent is evaporated completely, be placed in true
Moisture and other impurity for being adsorbed on sample surfaces are sloughed for 80 DEG C in empty drying box.Then this sample is placed in hydrogen in tube furnace
Continue reduction 4 hours for 300 DEG C in atmosphere.
Obtained material is mesoporous carbon-silica material palladium catalyst, has the structure (space group of two-dimentional six sides
P6mm), aperture 10.2nm, Kong Rongwei 0.75cm3/ g, specific surface area 427m2/ g, the load capacity of palladium are 1%, Pd nano particle ruler
Very little is 1.5nm.
Its distinctive X-ray diffraction (XRD) map such as Fig. 3.Its transmission electron microscope figure (TEM) is as shown in Figure 4.
43mg palladium catalyst is placed in 25mL round-bottom reaction flask, sequentially add thereto 8- methylquinoline (59mg,
0.4mmol), 142mg iodobenzene acetate, 10mL methanol is as solvent.Spherical condensation tube is connected, oil bath environment is then placed it in
Under, it increases temperature and starts to be stirred to react to 150 DEG C.After reaction, it is cooled to room temperature.Reaction solution is carried out with gas chromatograph
Analysis, the yield for obtaining 8- methoxyl methyl quinoline is 80%.
Embodiment 4
At 40-60 DEG C, the F108 (EO of 3.2g132PO50EO132) surfactant is dissolved in 8.0g toluene solution, then
1g 2mol/L hydrochloric acid solution is added, stirs prehydrolysis 2 hours, obtains solution A.At identical temperature, in 8.0g toluene solution successively
3.5g methyl orthosilicate is added, 0.6g 3- ureido-propyl trimethoxy silane stirs 2 hours, obtains solution B.Solution A and B solution
After mixing, the phenolic resin synthesized in addition 20wt% embodiment 1, magnetic agitation 2 hours.The clarification for obtaining light yellow clear is molten
Liquid.Above-mentioned solution is uniformly layered on glass culture dish surface, places 4 hours at room temperature, later, temperature is risen into 120 DEG C of hot polymerizations
24 hours, flaxen transparent membrane is scraped, i.e. preformed material.
Preformed material inertia protection gas is calcined 6 hours removing surfactants by 400 DEG C.
It weighs the above-mentioned solid sample of 0.5g to be placed in moderate beaker, the palladium nitrate palladium solution (1g/ of 6.6mL is added
100mL).Sealing places it in constant temperature oscillator, and concussion is uniform at room temperature.It then takes out and is placed on indoor solvent flashing, to molten
After agent is evaporated completely, it is placed in a vacuum drying oven 80 DEG C and sloughs moisture and other impurity for being adsorbed on sample surfaces.Then by this sample
Product are placed in tube furnace in atmosphere of hydrogen and restore 4 hours for 400 DEG C.
Obtained material is mesoporous carbon-silica material load palladium chtalyst.Structure (space group with two-dimentional six sides
P6mm), aperture 9.1nm, Kong Rongwei 0.92cm3/ g, specific surface area 580m2/ g, the load capacity of palladium are 3%, Pd nanoparticle size
For 3.5nm.
Its distinctive X-ray diffraction (XRD) map is as shown in Figure 5.
43mg palladium catalyst is placed in 25mL round-bottom reaction flask, sequentially add thereto 8- methylquinoline (59mg,
0.4mmol), 142mg iodobenzene acetate, 10mL methanol is as solvent.Spherical condensation tube is connected, oil bath environment is then placed it in
Under, it increases temperature and starts to be stirred to react to 150 DEG C.After reaction, it is cooled to room temperature.Reaction solution is carried out with gas chromatograph
Analysis, the yield for obtaining 8- methoxyl methyl quinoline is 75%.
Embodiment 5
At 40-60 DEG C, the F127 surfactant of 2.0g is dissolved in 10.0g acetaldehyde solution, and 2g0.5mol/ is then added
L hydrochloric acid solution stirs prehydrolysis 1 hour, obtains solution A.At identical temperature, 3.0g is being sequentially added in 10.0g acetaldehyde solution just
Silicic acid propyl ester, 0.4g 3- ureido-propyl trimethoxy silane stir 2 hours, obtain solution B.After solution A and B solution mixing, add
Enter the phenolic resin synthesized in 20wt% embodiment 1, magnetic agitation 4 hours.Obtain the clear solution of light yellow clear.It will be above-mentioned
Solution is uniformly layered on glass culture dish surface, places 1 hour at room temperature, later, temperature is risen to 100 DEG C of hot polymerizations 24 hours, will
Flaxen transparent membrane scrapes, i.e. preformed material.
Preformed material inertia protection gas is calcined 6 hours removing surfactants by 400 DEG C.
It weighs the above-mentioned solid sample of 0.5g to be placed in moderate beaker, the chlorine palladium acid sodium solution (1g/ of 2.2mL is added
100mL).Sealing places it in constant temperature oscillator, and concussion is uniform at room temperature.Solution of potassium borohydride is proportionally added into after taking-up,
It continuously adds and shakes up half an hour in constant temperature oscillator.It then takes out and is placed on indoor solvent flashing, after solvent is evaporated completely, be placed in true
Moisture and other impurity for being adsorbed on sample surfaces are sloughed for 80 DEG C in empty drying box.Then this sample is placed in hydrogen in tube furnace
Continue reduction 4 hours for 300 DEG C in atmosphere.
Obtained material is mesoporous carbon-silica material load palladium chtalyst.Structure (space group with two-dimentional six sides
P6mm), aperture 7.2nm, Kong Rongwei 0.7cm3/ g, specific surface area 564m2/ g, the load capacity of palladium are 1%, Pd nanoparticle size
For 1.0nm.
Its distinctive X-ray diffraction (XRD) map is as shown in Figure 6.
43mg palladium catalyst is placed in 25mL round-bottom reaction flask, sequentially add thereto 8- methylquinoline (59mg,
0.4mmol), 142mg iodobenzene acetate, 10mL methanol is as solvent.Spherical condensation tube is connected, oil bath environment is then placed it in
Under, it increases temperature and starts to be stirred to react to 150 DEG C.After reaction, it is cooled to room temperature.Reaction solution is carried out with gas chromatograph
Analysis, the yield for obtaining 8- methoxyl methyl quinoline is 87%.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium, which is characterized in that this method is,
Using soluble resin as carbon source, organic silicon source is organo-functional group source, and surfactant is template, and inorganic silicon is added
Source prepares ordered mesoporous polymer-silica composite material of amino functional by the polynary method assembled altogether；
Amino functional mesoporous carbon-silica composite material is obtained through calcining；
Further, dip loading Pd loads to Pd on mesoporous composite material；
Most product is obtained through reduction afterwards.
2. a kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium according to claim 1, special
Sign is that the soluble resin is resol resin of the molecular weight between 200-5000g/mol.
3. a kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium according to claim 1, special
Sign is that the organic silicon source is selected from N, N- bis- (3- trimethoxy silicon propyl) urea, 3- ureido-propyl trimethoxy silane, 3- urea
One of base propyl-triethoxysilicane, 3- TSL 8330,3-aminopropyltriethoxysilane are more
Kind.
4. a kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium according to claim 1, special
Sign is that the inorganic silicon source is selected from one of ethyl orthosilicate, methyl orthosilicate or positive silicic acid propyl ester or a variety of.
5. a kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium according to claim 1, special
Sign is that the surfactant is nonionic surfactant, is selected from polyethylene oxide-polypropylene oxide triblock copolymer
One of object or alkane-polyethylene oxide diblock copolymer surfactant are a variety of, and general formula can use CaH2a+ 1EOb、EOcPOdEOcIt indicates, wherein a numberical range is 10-18, b 5-25, c 5-135, d 25-135.
6. a kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium according to claim 1, special
Sign is, specifically includes the following steps:
(1) it dissolves each other surfactant and hydrochloric acid to obtain solution A, be obtained with organic solvent hydrolysis inorganic silicon source and organic silicon source molten
Solution A and solution B are mixed and added into soluble resin and reacted by liquid B, and the organic solvent contained in reactant is removed,
Obtain solid；
(2) solid for obtaining step (1) carries out low temperature thermosetting, preformed material is obtained, by preformed material in inert atmosphere protection
Lower calcining removes surfactant, obtains catalyst material predecessor；
(3) the catalyst material predecessor of step (2) is mixed with palladium ion solution, solid is obtained by filtration, is obtained by reduction
The mesoporous carbon-silica catalyst material of supported palladium.
7. a kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium according to claim 6, special
Sign is,
The organic solvent is selected from one of alcohols, benzene class, tetrahydrofuran, ether or methylene chloride or a variety of；
The mass concentration of surfactant is 0.5%-25% in step (1), and the concentration of hydrochloric acid solution is 0.2-4mol/L, inorganic
The molar ratio of silicon source and organic silicon source is 1-20, and the dosage molar ratio of organic silicon source and surfactant is 10-60, solubility tree
The molar ratio of rouge and total silicon source is 0.01-0.6；
Hydrolysis temperature is 20-45 DEG C, hydrolysis time 0.5-4h in step (1), and reaction temperature is 20~45 DEG C, and the reaction time is
10min-4h。
8. a kind of preparation method of the mesoporous carbon-silica catalyst material of supported palladium according to claim 6, special
Sign is,
Step (2) low temperature thermoset temperature is 40-120 DEG C, and the low temperature thermosetting time is 12-48h, and calcination temperature is 200-500 DEG C, is forged
Burning temperature is 1-12h；
Step (3) is using hydrogen reducing or using formalin, sodium borohydride solution or solution of potassium borohydride low-temperature reduction；
Palladium ion solution in step (3) is selected from palladium acetate, palladium nitrate, two ammino palladium of dichloro, four ammino palladium of dichloro, chlorine palladium acid sodium
Or one of chlorination palladium reagent or a variety of.
9. a kind of catalyst material being prepared such as the described in any item preparation methods of claim 1-8, which is characterized in that should
Catalyst material has six side's mesoscopic structure of two dimension of high-sequential, and specific surface area is 300~900m2/ g, Kong Rongwei 0.30~
2.0cm3/ g, aperture are 5.0~15.0nm, and metal Pd content is 1~10wt%, and Pd nanoparticle size is 1~5.0nm.
10. catalyst material as claimed in claim 9 generates 8- methoxyl methyl quinoline in 8- methylquinoline and methanol reaction
Using.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111790351A (en) * | 2020-06-24 | 2020-10-20 | 上海应用技术大学 | Preparation method of graded porous carbon material with toluene adsorption effect |
| CN114349885A (en) * | 2021-12-03 | 2022-04-15 | 国家能源集团宁夏煤业有限责任公司 | Preparation method of catalyst carrier, supported catalyst and application thereof |
| CN114836629A (en) * | 2022-05-05 | 2022-08-02 | 昆明贵研新材料科技有限公司 | Enrichment method of waste silicon dioxide carrier noble metal catalyst |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583331A (en) * | 2004-06-10 | 2005-02-23 | 复旦大学 | Preparing method for medium hole noble metal hollow microscapsule |
| CN102091626A (en) * | 2010-12-31 | 2011-06-15 | 南京工业大学 | Catalyst for catalytic hydrogenation of p-nitrophenol and preparation method thereof |
| CN102658200A (en) * | 2012-04-25 | 2012-09-12 | 上海师范大学 | Sulfonic acid-functionalized ordered mesoporous polymer-silicon oxide composite material and synthetic method thereof |
| CN103537304A (en) * | 2013-08-24 | 2014-01-29 | 北京化工大学 | Preparation of silane coupling agent-modified SiO2 loaded rhodium catalyst and selective hydrogenation application of catalyst to butadiene-acrylonitrile rubber |
| CN106334579A (en) * | 2016-08-23 | 2017-01-18 | 上海师范大学 | Recoverable ligand-free mesoporous polymer palladium catalyst and synthetic method and application thereof |
| CN106345461A (en) * | 2016-08-23 | 2017-01-25 | 上海师范大学 | Large-pore-size mesoporous carbon/silicon dioxide loaded gold nano-catalyst and synthesis method thereof |
| CN106345458A (en) * | 2016-08-23 | 2017-01-25 | 上海师范大学 | Mesoporous carbon-silicon dioxide complex loaded nano-palladium catalyst and synthesis method thereof |
| CN106517216A (en) * | 2016-11-03 | 2017-03-22 | 北京化工大学 | Biodegradable mesoporous carbon and silicon nano-sphere and method for preparing same |
| US20170362181A1 (en) * | 2014-12-05 | 2017-12-21 | Virginia Commonwealth University | Chelation directed c-h activation reactions catalyzed by solid-supported palladium(ii) catalysts |
| CN109420515A (en) * | 2017-08-21 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of high-dispersion loading type metallic catalyst |
-
2019
- 2019-04-30 CN CN201910358799.4A patent/CN110075900B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583331A (en) * | 2004-06-10 | 2005-02-23 | 复旦大学 | Preparing method for medium hole noble metal hollow microscapsule |
| CN102091626A (en) * | 2010-12-31 | 2011-06-15 | 南京工业大学 | Catalyst for catalytic hydrogenation of p-nitrophenol and preparation method thereof |
| CN102658200A (en) * | 2012-04-25 | 2012-09-12 | 上海师范大学 | Sulfonic acid-functionalized ordered mesoporous polymer-silicon oxide composite material and synthetic method thereof |
| CN103537304A (en) * | 2013-08-24 | 2014-01-29 | 北京化工大学 | Preparation of silane coupling agent-modified SiO2 loaded rhodium catalyst and selective hydrogenation application of catalyst to butadiene-acrylonitrile rubber |
| US20170362181A1 (en) * | 2014-12-05 | 2017-12-21 | Virginia Commonwealth University | Chelation directed c-h activation reactions catalyzed by solid-supported palladium(ii) catalysts |
| CN106334579A (en) * | 2016-08-23 | 2017-01-18 | 上海师范大学 | Recoverable ligand-free mesoporous polymer palladium catalyst and synthetic method and application thereof |
| CN106345461A (en) * | 2016-08-23 | 2017-01-25 | 上海师范大学 | Large-pore-size mesoporous carbon/silicon dioxide loaded gold nano-catalyst and synthesis method thereof |
| CN106345458A (en) * | 2016-08-23 | 2017-01-25 | 上海师范大学 | Mesoporous carbon-silicon dioxide complex loaded nano-palladium catalyst and synthesis method thereof |
| CN106517216A (en) * | 2016-11-03 | 2017-03-22 | 北京化工大学 | Biodegradable mesoporous carbon and silicon nano-sphere and method for preparing same |
| CN109420515A (en) * | 2017-08-21 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of high-dispersion loading type metallic catalyst |
Non-Patent Citations (1)
| Title |
|---|
| YUAN YANG ET AL.: ""Three dimensional composites of graphene as supports in Pd-catalyzed synthetic applications"", 《REACTION CHEMISTRY & ENGINEERING》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111790351A (en) * | 2020-06-24 | 2020-10-20 | 上海应用技术大学 | Preparation method of graded porous carbon material with toluene adsorption effect |
| CN114349885A (en) * | 2021-12-03 | 2022-04-15 | 国家能源集团宁夏煤业有限责任公司 | Preparation method of catalyst carrier, supported catalyst and application thereof |
| CN114349885B (en) * | 2021-12-03 | 2023-11-07 | 国家能源集团宁夏煤业有限责任公司 | Preparation method of catalyst carrier, supported catalyst and application thereof |
| CN114836629A (en) * | 2022-05-05 | 2022-08-02 | 昆明贵研新材料科技有限公司 | Enrichment method of waste silicon dioxide carrier noble metal catalyst |
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